The role of hydrogen in hydrogenated microcrystalline silicon film and in deposition process with VHF-PECVD technique

The role of hydrogen in hydrogenated microcrystalline silicon （μc-Si：H） thin films in deposition processes with very high frequency plasma-enhanced chemical vapour deposition （VHF-PECVD） technique have been investigated in this paper. With in situ optical emission spectroscopy （OES） diagnosis during the fabrication of μc-Si：H thin films under different plasma excitation frequency Ve （60MHz-90MHz）, the characteristic peak intensities （IsiH＊, IHα＊ and IHβ＊ ） in SiH4＋H2 plasma and the ratio of （IHα＊ ＋ IHβ＊ ） to IsiH＊ were measured; all the characteristic peak intensities and the ratio （IHα＊ ＋ IHβ＊ ）/IsiH＊ are increased with plasma excitation frequency. It is identified that high plasma excitation frequency is favourable to promote the decomposition of SiH4＋H2 to produce atomic hydrogen and SiHx radicals. The influences of atomic hydrogen on structural properties and that of SiHx radicals on deposition rate of μc-Si：H thin films have been studied through Raman spectra and thickness measurements, respectively. It can be concluded that both the crystalline volume fraction and deposition rate are enhanced with the increase of plasma excitation frequency, which is in good accord with the OES results. By means of FTIR measurements, hydrogen contents of μc-Si：H thin films deposited at different plasma excitation frequency have been evaluated from the integrated intensity of wagging mode near 640 cm^-1. The hydrogen contents vary from 4% to 5%, which are much lower than those of μc-Si：H films deposited with RF-PECVD technique. This implies that μc-Si：H thin films deposited with VHF-PECVD technique usually have good stability under light-soaking.     

Influence of ignition condition on the growth of silicon thin films using plasma enhanced chemical vapour deposition

The influences of the plasma ignition condition in plasma enhanced chemical vapour deposition (PECVD) on the interfaces and the microstructures of hydrogenated microcrystalline Si (μc-Si:H) thin films are investigated.The plasma ignition condition is modified by varying the ratio of SiH 4 to H 2 (R H).For plasma ignited with a constant gas ratio,the time-resolved optical emission spectroscopy presents a low value of the emission intensity ratio of Hα to SiH (I Hα /I SiH) at the initial stage,which leads to a thick amorphous incubation layer.For the ignition condition with a profiling R H,the higher I Hα /I SiH values are realized.By optimizing the R H modulation,a uniform crystallinity along the growth direction and a denser μc-Si:H film can be obtained.However,an excessively high I Hα /I SiH may damage the interface properties,which is indicated by capacitance-voltage (C-V) measurements.Well controlling the ignition condition is critically important for the applications of Si thin films.     

Growth characteristics of amorphous-layer-free nanocrystalline silicon films fabricated by very high frequency PECVD at 250 ℃

Amorphous-layer-free nanocrystalline silicon films were prepared by a very high frequency plasma enhanced chemical vapor deposition(PECVD) technique using hydrogen-diluted SiH4 at 250 C.The dependence of the crystallinity of the film on the hydrogen dilution ratio and the film thickness was investigated.Raman spectra show that the thickness of the initial amorphous incubation layer on silicon oxide gradually decreases with increasing hydrogen dilution ratio.High-resolution transmission electron microscopy reveals that the initial amorphous incubation layer can be completely eliminated at a hydrogen dilution ratio of 98%,which is lower than that needed for the growth of amorphous-layer-free nanocrystalline silicon using an excitation frequency of 13.56 MHz.More studies on the microstructure evolution of the initial amorphous incubation layer with hydrogen dilution ratios were performed using Fourier-transform infrared spectroscopy.It is suggested that the high hydrogen dilution,as well as the higher plasma excitation frequency,plays an important role in the formation of amorphous-layer-free nanocrystalline silicon films.     

Surface properties of diamond-like carbon films prepared by CVD and PVD methods

Diamond-like carbon （DLC） films have been deposited using three different techniques： （a） electron cyclotron resonance——plasma source ion implantation, （b） low-pressure dielectric barrier discharge, （c） filtered——pulsed cathodic arc discharge, The surface and mechanical properties of these films are compared using atomic force microscopebased tests. The experimental results show that hydrogenated DLC films are covered with soft surface layers enriched with hydrogen and sp^3 hybridized carbon while the soft surface layers of tetrahedral amorphous carbon （ta-C） films have graphite-like structure, The formation of soft surface layers can be associated with the surface diffusion and growth induced by the low-energy deposition process. For typical CVD methods, the atomic hydrogen in the plasmas can contribute to the formation of hydrogen and sp^3 hybridized carbon enriched surface layers, The high-energy ion implantation causes the rearrangement of atoms beneath the surface layer and leads to an increase in film density. The ta-C films can be deposited using the medium energy carbon ions in the highly-ionized plasma.     

Research on the boron contamination at the p/i interface of microcrystalline silicon solar cells deposited in a single PECVD chamber

This paper studies boron contamination at the interface between the p and i layers of μc-Si:H solar cells deposited in a single-chamber PECVD system. The boron depth profile in the i layer was measured by Secondary Ion Mass Spectroscopy. It is found that the mixed-phase μc-Si:H materials with 40% crystalline volume fraction is easy to be affected by the residual boron in the reactor. The experimental results showed that a 500-nm thick μc-Si:H covering layer or a 30-seconds of hydrogen plasma treatment can effectively reduce the boron contamination at the p/i interface. However, from viewpoint of cost reduction, the hydrogen plasma treatment is desirable for solar cell manufacture because the substrate is not moved during the hydrogen plasma treatment.     

Measurement and Analysis of Composition and Depth Profile of H in Amorphous Si1-xCx:H Films

Composition in amorphous Si1-xCx：H heteroepitaxial thin films on Si （100） by plasma enhanced chemical vapour deposition （PECVD） is analysed. The unknown x （0.45-3.57） and the depth profile of hydrogen in the thin films are characterized by Rutherford backscattering spectrum （RBS）, resonance-nuclear reaction analysis （R-NRA） and elastic recoil detection （ERD）, respectively. In addition, the depth profile of hydrogen in the unannealed thin films is compared to that of the annealed thin films with rapid thermal annealing （RTA） or laser spike annealing （LSA） in nitrogen atmosphere. The results indicate that the stoichiometric amorphous SiC can be produced by PECVD when the ratio of CH4/SiH4 is approximately equal to 25. The content of hydrogen decreases suddenly from 35% to 1% after 1150℃ annealing. RTA can reduce hydrogen in SiC films effectively than LSA.     

Effects of deposition pressure and plasma power on the growth and properties of boron-doped microcrystalline silicon films

Using diborane as doping gas, p-doped μc-Si：H layers are deposited by using the plasma enhanced chemical vapour deposition （PECVD） technology. The effects of deposition pressure and plasma power on the growth and the properties of μc-Si：H layers are investigated. The results show that the deposition rate, the electrical and the structural properties are all strongly dependent on deposition pressure and plasma power. Boron-doped μc-Si：H films with a dark conductivity as high as 1.42 Ω^-1·cm^-1 and a crystallinity of above 50% are obtained. With this p-layer, μc-Si：H solar cells are fabricated. In addition, the mechanism for the effects of deposition pressure and plasma power on the growth and the properties of boron-doped μc-Si：H layers is discussed.     

Optical emission spectroscopy study on deposition process of microcrystalline silicon

This paper reports that the optical emission spectroscopy （OES） is used to monitor the plasma during the deposition process of hydrogenated microcrystalline silicon films in a very high frequency plasma enhanced chemical vapour deposition system. The OES intensities （Sill^＊, H^＊ and H^＊β） are investigated by varying the deposition parameters. The result shows that the discharge power, silane concentrations and substrate temperature affect the OES intensities. When the discharge power at silane concentration of 4% increases, the OES intensities increase first and then are constant, the intensities increase with the discharge power monotonously at silane concentration of 6%. The SiH^＊ intensity increases with silane concentration, while the intensities of H^＊α and H^＊β increase first and then decrease. When the substrate temperature increases, the SiH^＊ intensity decreases and the intensities of H^＊α and H^＊β are constant. The correlation between the intensity ratio of IH^＊α/ISiH^＊ and the crystalline volume fraction （Xc） of films is confirmed.     

Influence of the deposition parameters on the transition region of hydrogenated silicon films growth

Hydrogenated microcrystalline and amorphous silicon thin films were prepared by very high frequency plasmaenhanced chemical vapour deposition （VHF PECVD） by using a mixture of silane and hydrogen as source gas. The influence of deposition parameters on the transition region of hydrogenated silicon films growth was investigated by varying the silane concentration （SC）, plasma power （Pw）, working pressure （P）, and substrate temperature （Ts）. Results suggest that SC and Ts are the most critical factors that affect the film structure transition from microcrystalline to amorphous phase. A narrow region in the range of SC and Ts, in which the rapid phase transition takes place, was identified. It was found that at lower P or higher Pw, the transition region is shifted to larger SC. In addition, the dark conductivity and photoconductivity decrease with SC and show sharp changes in the transition region. It proposed that the transition process and the transition region are determined by the competition between the etching effect of atomic hydrogen and the growth of amorphous phase.     

Evolution of infrared spectra and optical emission spectra in hydrogenated silicon thin films prepared by VHF-PECVD

A series of hydrogenated silicon thin films with varying silane concentrations have been deposited by using very high frequency plasma enhanced chemical vapor deposition (VHF-PECVD) method.The deposition process and the silicon thin films are studied by using optical emission spectroscopy (OES) and Fourier transfer infrared (FTIR) spectroscopy,respectively.The results show that when the silane concentration changes from 10% to 1%,the peak frequency of the Si-H stretching mode shifts from 2000 cm-1 to 2100 cm-1,while the peak frequency of the Si-H wagging-rocking mode shifts from 650 cm-1 to 620 cm-1.At the same time the SiH /H α intensity ratio in the plasma decreases gradually.The evolution of the infrared spectra and the optical emission spectra demonstrates a morphological phase transition from amorphous silicon (a-Si:H) to microcrystalline silicon (μc-Si:H).The structural evolution and the μc-Si:H formation have been analyzed based on the variation of H α and SiH* intensities in the plasma.The role of oxygen impurity during the plasma process and in the silicon films is also discussed in this study.     

VHF-PECVD低温制备微晶硅薄膜的拉曼散射光谱和光发射谱研究

采用拉曼散射光谱和PR650光谱光度计对VHF-PECVD制备的微晶硅薄膜进行了结构表征和在线监测研究.结果表明：功率对材料的晶化率（χc）有一定的调节作用，硅烷浓度大，微调作用更明显；SiH*的强度只能在一定的范围内表征材料的沉积速率，功率大相应的速率反而下降；I［Hα*］/I［SiH*］强度比值反映了材料晶化程度，此结果和拉曼散射光谱测试结果显示出一致性；I［Hβ*］/I［Hα*］的强度比表明氢等离子体中的电子温度随功率的增大而逐渐降低. 关键词： 甚高频等离子体增强化学气相沉积 微晶硅 拉曼散射谱 光发射谱     

VHF等离子体光发射谱(OES)的在线监测

采用光发射谱(OES)测量技术，对不同制备条件下的甚高频(VHF)等离子体辉光进行了在线监 测.实验表明，VHF等离子体中特征发光峰(Si，SiH,H_α,H^*_β 等)的强度较常规的射 频(RF)等离子体明显增强，并且在制备μc-Si：H的工艺条件下(H稀释度R(H₂/S iH₄)=23 )，随激发频率的增加而增大，这些发光峰的变化趋势与材料沉积速率的变化规律较相似.Si H峰等的强度随气压的变化则因硅烷H稀释度及功率的不同而异：高H稀释(R=23)时，SiH峰强 度在低辉光功率下随反应气压的增大单调下降，在高辉光功率下随气压的变化呈现类高斯规 律；低H稀释(R=5．7)时， SiH峰随气压的变化基本上是单调下降的，下降速率也与功率有 关，这些结果表明，VHF-PECVD制备μc-Si：H和a-Si：H的反应动力学过程存在较大差异.此 外，随着激发功率的增大，Si，SiH峰都先迅速增大然后趋于饱和，并且随着H稀释率的增大 ，将更快呈现饱和现象.通过对OES结果的分析与讨论可知，VHF-PECVD技术沉积硅基薄膜可 以有效提高沉积速率，而且，硅基薄膜的沉积速率的进一步提高需要综合考虑H稀释度、气 压和功率等的匹配与优化. 关键词： 甚高频等离子体化学气相沉积 氢化硅薄膜 光发射谱     

氮流量在高氢氛围中对富硅氮化硅薄膜材料结构及其发光特性的影响

采用等离子体增强化学气相沉积技术,以N_2掺入到SiH_4和H_2的沉积方式,分别在玻璃和N型单晶硅片(100)衬底上制备富硅氮化硅薄膜。通过紫外-可见光吸收光谱、傅里叶变换红外吸收光谱(FTIR光谱)、拉曼光谱和光致发光谱(PL谱)分别表征掺氮硅薄膜材料的带隙、结构及其发光特性的变化。结果表明:在氢气的氛围中,随着氮气流量的增加,氢原子能够对薄膜缺陷起到抑制作用,并使较低的SiH_4/N_2流量比下呈现富硅态,但却不利于硅团簇的形成。随着氮原子的掺入,Si-N键的含量增大,带隙增大,薄膜内微结构的无序度也增大,薄膜出现了硅与氮缺陷相关的缺陷态发光;随着氮原子进一步增加,出现了带尾态发光,进一步讨论了发光与结构之间的关联。这些结果有助于采用PEXVD制备富硅氮化硅对材料发光与结构特性的优化。     

Fabrication of high growth rate solar-cell-quality μc-Si:H thin films by VHF-PECVD

Several series of Si:H films were fabricated by the very high frequency plasma enhanced chemical vapour deposition (VHF-PECVD) at different substrate temperatures (T_s) and silane concentration (SC=[SiH_4]/[SiH_4+H_2]%). The results of Raman spectroscopy showed structural evolution of the Si:H films with the variation of T_s and SC. The results of x-ray diffraction (XRD) measurements indicated that T_s also influences the crystal orientation of the Si:H films. The modulation effect of T_s on crystalline volume fraction (X_c) is more evident for the high SC, which shows different trend compared to low SC. In addition, the growth rate of the films also showed a regular change with the variation of SC and T_s. Different samples in the series showed a similar increase in dark conductivity and a decrease in photosensitivity with increasing T_s and decreasing SC. Device-quality microcrystalline silicon materials were deposited at a high growth rate, characterized by relatively low dark conductivity and relatively high photosensitivity in a certain crystalline range. The microcrystalline silicon solar cell with a conversion efficiency of 4.55% has been prepared by VHF-PECVD.     

Preparation of hydrogenated microcrystalline silicon films with hot-wire-assisted MWECR-CVD system

Intrinsic hydrogenated microcrystalline silicon （μc-Si：H） films have been prepared by hot-wire-assisted microwave electron-cyclotron-resonance chemical vapour deposition （HW-MWECR-CVD） under different deposition conditions, Fourier-transform infrared spectra and Raman spectra were measured. Optical band gap was determined by Tauc plots, and experiments of photo-induced degradation were performed. It was observed that hydrogen dilution plays a more essential role than substrate temperature in microcrystalline transformation at low temperatures. Crystalline volume fraction and mean grain size in the films increase with the dilution ratio （R=H2/（H2＋SiH4））. With the rise of crystallinity in the films, the optical band gap tends to become narrower while the hydrogen content and photo-induced degradation decrease dramatically. The samples, were identified as μc-Si：H films, by calculating the optical band gap. It is considered that hydrogen dilution has an effect on reducing the crystallization activation energy of the material, which promotes the heterogeneous solid-state phase transition characterized by the Johnson-Mehl-Avrami （JMA） equation. The films with the needed structure can be prepared by balancing deposition and crystallization through controlling process parameters.     

EACVD中的Hα谱线与最佳生长条件

采用蒙特卡罗方法,模拟了CH4/H2混合气体为源气体的EACVD中的氢原子发射过程。考虑了电子与H2的弹性碰撞及振动激发、分解、电子激发、相应于Hα,Hβ,Hγ谱线的激发、电离及分解电离等非弹性碰撞过程;与CH4的碰撞考虑了弹性动量传输及振动激发、分解、电子激发、电离及分解电离等非弹性碰撞过程。研究了不同实验条件下产生的H,CH3的数目与Hδ谱线强度的关系,给出了一种通过Hα谱线来推断生长金刚石薄膜的最佳实验条件的方法。     

甚高频电容耦合氢等离子体特性研究

采用高H₂稀释的SiH₄等离子体放电, 特别是甚高频等离子体增强化学气相沉积技术是当前高速制备优质微晶硅薄膜的主流方法. 尽管在实验上取得了很大的突破, 但其沉积机理一直是研究的热点和难点. 本文通过建立二维时变的轴对称模型,在75 MHz放电频率下, 对与微晶硅沉积非常相关的甚高频电容耦合氢等离子体放电进行了数值模拟, 研究了沉积参数对等离子体特性的影响, 并与光发射谱(OES)在线监测结果进行了比较. 结果表明: 电子浓度 n_e在等离子体体层中间区域最大, 而电子温度 T_e及H_α与H_β的数密度在体层和鞘层界面附近取极大值; 当气压从1 Torr (1 Torr=133.322 Pa)增大至5 Torr时, 等离子体电势单调降低, 在体层中间区域 n_e先快速增大然后逐渐减小, T_e先下降后趋于稳定; 随着放电功率从30 W增大到70 W, 电子浓度 n_e及H_α与H_β的数密度均线性增大, 而电子温度 T_e基本保持不变; OES在线分析结果与模拟结果符合得很好.